Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
  • G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
  • G01N31/168—Determining water content by using Karl Fischer reagent

Definitions

• the usual method for quantitatively determining water is the Karl-Fischer method in which the substance to be analyzed is reacted with sulfur dioxide and iodine dissolved in a mixture of pyridine and methanol; see K. Fischer, Angew. Chemie, vol. 48 (1935), page 394.
• the reagent reacts with water to give pyridine sulfate and hydrogen iodide. In this process the reagent undergoes decoloration.
• the iodine consumption is a measure for the water content of the substance.
• the reaction pro- ceeds according to the following equation: !
• the titrimetric determination is very accurate.
• the reagent allows a water content of less than 0.01% to be detected; see Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd edition, vol. 2 (1963), pages 673-677.
• a disadvantage of the Karl-Fischer method is the fact that the reaction proceeds slowly, that titration is therefore laborious and time-consuming and that the end-point is distorted.
• An inconvenience is the annoying odor caused by the sulfur dioxide and pyridine.
• pyridine makes it necessary to perform the process under a fume hood.
• Another disadvantage is the yellow SO 2 1 complex formed by the sulfur dioxide and iodide which excludes the visual determination of the end point.
• esterification reaction takes place: methanol + acetic acid ⁇ methyl acetate + water.
• the present invention is based on the surprising finding that the presence of 2-methoxyethanol, methanol or a mixture thereof and an alkali metal salt of the trimethyl acetic acid (pivalic acid, molecular weight 102.12; (CH 3 ) 3 CCOOH) or a mixture of an alkali metal pivalate and an alkali metal salicylate significantly reduce the ester reaction in the solution A. Therefore, according to the invention an alkali metal salt of the trimethyl acetic acid (pivalic acid) is used instead of the alkali metal acetate employed in the above described known improved method. It was further found that the additional use of an alkali metal salt of salicylic acid further curtails the ester reaction.
• solution A for instance, the molarity of sodium pivalate (trimethyl acetic acid - sodium salt) is 1 and the molarity of sulfur dioxide is 0.4.
• the color of the solution is 10 and the blind value is 0 to 4 ml of the titrating solution B per 20 ml of solution A.
• the titrating solution B has a constant titer of 3.5 mg H 2 0/ml. About 1 part of titrating solution B is needed per 2 parts of solution A.
• the titration procedure is as follows: 20 ml of solution A are pretitrated with the titrating solution B under steady stirring and with moisture being excluded. A specified amount of the water-containing substance to be analyzed is then quickly placed into the titration vessel. The amount of the substance to be analyzed (amount of test sample) is to be adequately proportioned to the estimated amount of water present.
• the bipotentiometric method is used in the most usual titrations for determining the end point.
• the reduction time is normally 20 seconds, at which time the point of equivalence is reached.
• the problem underlying the invention is to develop an improved reagent for the quantitative determination of water.
• This reagent is based on the above-described known reagent solution A which is used together with the titrating solution B. When allowed to stand, the reagent forms minor precipitates only slowly even at elevated temperatures while at the same time the increase of the blind value is minimized.
• the invention relates to a reagent for the quantitative determination of water used together with an iodine-containing titrating solution, the reagent containing sulfur dioxide and an anhydrous alkali metal salt of the trimethyl acetic acid in 2-methoxyethanol, methanol or a mixture thereof as solvent, the volume ratio of a mixture of 2-methoxy ethanol and methanol being at least 10 : 90.
• the reagent (reagent solution A) additionally contains an alkali metal salicylate. This reagent (solution A) is used together with the above-described titrating solution B in a known manner for the quantitative determination of water.
• the solution A of the invention preferably contains the anhydrous lithium or sodium salts as alkali metal trimethyl acetate and optionally alkali metal salicylate.
• the sodium salts are preferred for economic reasons.
• the alkali metal trimethyl acetate and the alkali metal salicylate optionally used serve above all as buffer.
• the alkali metal trimethyl acetate is employed in a molar amount of 1.5 to 0.5, preferably 1.2 to 0.8 and optimally 1.1 to 0.9.
• the alkali metal salicylate is used in a molar amount of 1.5 to 0.5, preferably 1.2 to 0.8, and optimally 1.1 to 0.9.
• the ratio of alkali metal trimethyl acetate to alkali metal salicylate is preferably 1 : 1.
• the solution A is preferably 1 molar,i.e. it can contain 0.5 mole of alkali metal trimethyl acetate and 0.5 mole of alkali metal salicylate.
• the sulfur dioxide is used in a molar amount of 0.7 to 0.1, preferably 0.5 to 0.2, optimally 0.45 to 0.35.
• the iodine is used in the titrating solution B in a molar amount of 0.3 to 0.1, preferably 0.25 to 0.15, and optimally 0.23 to 0.19.
• the reagent solutions contain the ingredients in amounts proportioned to each other.
• the solvent used for the solution A and the titrating solution B i.e. the 2-methoxy ethanol, the methanol or the mixture of 2-methoxy ethanol and methanol should preferably be anhydrous.
• anhydrous is understood here products with a water content of at most 0.05 percent by weight. Such products are commercially available.
• the volume ratio is at least 10 : 90, preferably 15 : 85 to 25 : 75.
• the titrating solution B is prepared in the following manner:
• the reagents of the invention keep well at room temperature in tightly sealed bottles.
• Nitrogen is blown into 158 kg of anhydrous methanol for 15 minutes under stirring. 12.4 kg of dried sodium trimethyl acetate and 16 kg of alkali metal salicylate are then added in small portions under stirring and dissolved. The solution obtained once the substances have completely dissolved is stirred while nitrogen is blown into it for another 15 minutes. 5.1 kg of sulfur dioxide are then slowly added within 4 hours, yielding solution A which can be used for the quantitative determination of water together with a titrating solution of iodine in methanol, 2-methoxy ethanol or in a mixture of 2-methoxy ethanol and methanol.
• the titrating solution B is prepared in the following manner:
• Solution A is prepared according to example 1, however a mixture of 120.1 kg of anhydrous methanol and 36.5 kg of anyhdrous 2-methoxy ethanol is used as well as 24.8 kg of dried sodium trimethyl acetate and 5.1 kg of sulfur dioxide.
• Example 2 is repeated, however a mixture of methanol and 2-methoxy ethanol is used in the volume ratio of 75 : 25 or 90 : 10.
• Examples 1 and 2 are repeated, however 20.4 kg of lithium trimethyl acetate are used instead of 24.8 kg of sodium trimethyl acetate and 10.2 kg of lithium trimethyl acetate instead of 12.4 kg of sodium trimethyl acetate, respectively.
• Example 1 is repeated, however 6.4 kg and not 5.1 kg of sulfur dioxide are used.
• Example 1 is repeated, however 3.2 kg and not 5.1 kg of sulfur dioxide are used.
• Nitrogen is blown for 15 minutes under stirring into a mixture of 120.1 kg of anhydrous methanol and 36.5 kg of anhydrous 2-methoxy ethanol.
• 15.6 kg of anhydrous sodium acetate which was dried for 24 hours at 150°C is then added in small portions under stirring and dissolved.
• the mixture obtained after the substances have completely dissolved is stirred while nitrogen is blown into it for another 15 minutes.
• 6.1 kg of sulfur dioxide are then slowly introduced within 4 hours.
• the resultant solution A can be used for the quantitative determination of water together with the titrating solution of iodine in methanol, 2-methoxy ethanol or in a mixture of 2-methoxy ethanol and methanol.
• the titrating solution B is prepared in the following manner:
• Comparative test 1 is repeated, however 3.33 kg and not 6.1 kg of sulfur dioxide are used.
• the table below shows the stability of the blind value (consumption of titrating solution B per 20 ml of solution A) of the solutions A prepared according to examples 1, 5 and 6 and comparative tests 1 and 2.
• the blind value remains stable thanks to the inventive composition of the reagent A, and consequently the problem posed of developing a stable solution A for each working temperature is successfully solved.
• the table also shows that the blind value is even more stable if the solution contains less sulfur dioxide (example 6).
• the reagent solution of example 1 and the titrating solution B is used for determining water in petroleum ether having a boiling point of 100 to 140°C.
• the test is carried out in the following manner:
• Test A is repeated with the reagent solution of example 4.
• the petroleum ether has a water content of 0.004 percent.
• the reagent solution of example 4 is used for the determination of water of technical acetone. 5 ml of acetone are placed into the titration vessel and take up 2.28 ml of titrating solution B. This corresponds to a 0.26 percent water content of the acetone.
• Test A is repeated with the reagent solution of example 1 and example 5. The following results are obtained:
• the water content of edible oil is determined in a further test using the reagent solution of example 5.
• the test is carried out in the following manner:

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• 1980
  • 1980-09-02 EP EP80105224A patent/EP0046819B1/de not_active Expired
  • 1980-09-02 AT AT80105224T patent/ATE11457T1/de not_active IP Right Cessation
  • 1980-09-02 DE DE8080105224T patent/DE3070017D1/de not_active Expired
• 1981
  • 1981-08-14 US US06/292,880 patent/US4355998A/en not_active Expired - Lifetime
  • 1981-08-18 CA CA000384104A patent/CA1171343A/en not_active Expired
  • 1981-08-26 AU AU74645/81A patent/AU548600B2/en not_active Ceased
  • 1981-09-01 JP JP56136191A patent/JPS5786048A/ja active Pending

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